CN113321284B - Method for treating arsenic-containing waste liquid and solidifying arsenic slag - Google Patents
Method for treating arsenic-containing waste liquid and solidifying arsenic slag Download PDFInfo
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- CN113321284B CN113321284B CN202110877908.0A CN202110877908A CN113321284B CN 113321284 B CN113321284 B CN 113321284B CN 202110877908 A CN202110877908 A CN 202110877908A CN 113321284 B CN113321284 B CN 113321284B
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- Prior art keywords
- arsenic
- waste
- slag
- water
- waste liquid
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- 239000002699 waste material Substances 0.000 title claims abstract description 146
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 121
- 239000007788 liquid Substances 0.000 title claims abstract description 100
- 239000002893 slag Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004568 cement Substances 0.000 claims abstract description 47
- 239000002351 wastewater Substances 0.000 claims abstract description 44
- 239000010881 fly ash Substances 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 239000004575 stone Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 86
- 239000000292 calcium oxide Substances 0.000 claims description 43
- 235000012255 calcium oxide Nutrition 0.000 claims description 43
- 239000004593 Epoxy Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 25
- 239000011575 calcium Substances 0.000 abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052791 calcium Inorganic materials 0.000 abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- 239000011737 fluorine Substances 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 239000002920 hazardous waste Substances 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 26
- 238000000498 ball milling Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002386 leaching Methods 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000000701 coagulant Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 229940000489 arsenate Drugs 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229960002594 arsenic trioxide Drugs 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 208000008316 Arsenic Poisoning Diseases 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B1/00—Dumping solid waste
- B09B1/004—Covering of dumping sites
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application relates to the technical field of hazardous waste treatment, and particularly discloses a method for treating arsenic-containing waste liquid and solidifying arsenic slag. The method comprises the following steps: step 1: adding a calcium source into the arsenic-containing waste liquid, and then carrying out solid-liquid separation to obtain waste water and waste residue; step 2: mixing the waste residue with a curing material and water, pressing and forming, and curing to obtain a cured body; the solidified material comprises cement, fly ash, slag and broken stone; the weight ratio of the waste residue to the solidified material is (1-3): (0.7-2); the water-cement ratio is 0.15-0.32. Adding a calcium source into the waste liquid, and reacting pollutants such as arsenic, fluorine and the like in the waste liquid with the calcium source to generate precipitate; solid-liquid separation, safe discharge of waste water, interaction of waste residue and cementing materials such as cement, fly ash and slag to form a solidified body, direct use of the solidified body in safe landfill, namely direct discharge of waste water after arsenic-containing waste liquid treatment, direct use of waste residue in safe landfill, and no secondary pollution to the environment.
Description
Technical Field
The application relates to the field of hazardous waste treatment, in particular to a method for treating arsenic-containing waste liquid and solidifying arsenic slag.
Background
Arsenic, the symbol of element As, is a non-metallic element, and the simple substance exists in the form of three allotropes, namely, ash arsenic, black arsenic and yellow arsenic. Arsenic is widely found in nature, and can be detected in soil, water, minerals and plants, and normal human tissues also contain trace arsenic. In daily life, people may take arsenic through food, water sources and the atmosphere, and research shows that a proper amount of arsenic is beneficial to synthesis of hemoglobin, but excessive arsenic can cause arsenic poisoning and damage the health of human bodies.
Along with the development of economy, the use of arsenic is more and more, the arsenic pollution is more and more serious, especially mining and smelting waste residues and industrial waste water discharged from metallurgy, chemical industry, pesticides, dyes, tanning, geothermal power plants and the like contain a large amount of arsenic, and the arsenic-containing waste water can not only harm the health of people, but also harm aquatic organisms and cause a lot of harm to human bodies and environment. Arsenic belongs to a national class of pollutants, the highest allowable emission concentration of which is 0.5mg/L, and therefore, arsenic-containing wastewater needs to be treated.
Currently, the commonly used arsenic removal technologies mainly include: chemical precipitation, coagulation precipitation, chemical adsorption and ion exchange, among others, electrocoagulation, biological, membrane treatment, oxidation and extraction. Among them, the most used and most common is the chemical precipitation method, which is based on the principle of precipitation separation from water by adding a metal ion to combine with arsenate to form an insoluble salt. As long as other metal ions exist in the solution and the ion product of the metal ions and arsenate radicals is larger than the solubility product, arsenic in water can be generated into arsenate precipitate to be separated and removed.
Disclosure of Invention
The application provides a method for treating arsenic-containing waste liquid and solidifying arsenic slag, which can reduce the arsenic content in the waste water and simultaneously can safely bury the waste slag without causing secondary pollution.
The application provides a method for treating arsenic-containing waste liquid and solidifying arsenic slag, which adopts the following technical scheme:
a method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding a calcium source into the arsenic-containing waste liquid, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: mixing the waste residue with a curing material and water, pressing and forming, and curing to obtain a cured body;
the solidified material comprises cement, fly ash, slag and broken stone;
the weight ratio of the waste residue to the solidified material is (1-3): (0.7-2);
the water-cement ratio is 0.15-0.32.
By adopting the technical scheme, the waste residue interacts with cementing materials such as cement, fly ash and slag, the activity of the cementing materials can be excited, and the waste residue is rapidly solidified to obtain a solidified body. In industrial application, the solidified body is used for safe landfill, so that the safe treatment of waste residue can be realized, and secondary pollution to the environment can not be caused. In the application, by controlling the components of the curing material, the proportion of the waste residue to the curing material, the water-cement ratio and the like, the curing body with high strength, good waterproof effect and low leaching rate can be obtained, and the curing body meets the requirements of curing and stabilizing hazardous wastes.
The calcium source may be quicklime (CaO) or slaked lime (Ca (OH)2) When the calcium source is added to treat the waste liquid, an excessive amount of the calcium source is added. The term "excess" as used herein means that sufficient calcium ions react with arsenic, fluorine and the like in the wastewater to remove the arsenic, fluorine and the like as much as possible from the wastewater. When the waste liquid is actually treated, the arsenic content in the waste liquid is firstly detected, then the theoretical adding amount of the required calcium source is calculated, and then the calcium source is added according to the theoretical adding amount. Preferably, in the application, the actual adding amount of the calcium source is 1.3-1.7 times of the theoretical adding amount of the calcium source.
Adding excessive quicklime or slaked lime, on one hand, enough calcium source is available, so that pollutants such as arsenic, fluorine and the like in the waste liquid can be removed as much as possible; on the other hand, the residual calcium source after the reaction with the pollution of arsenic, fluorine and the like can remove impurities of heavy metals and the like, thereby better purifying the sewage. Further, Ca (OH)2The waste slag solidifying agent is a slightly soluble substance, can be attached to the surface of waste slag, and can be used as a cement accelerating agent to accelerate cement solidification, thereby being beneficial to efficiently solidifying the waste slag.
The quick lime can adsorb impurities in sewage, can purify the sewage, is favorable for safe discharge of waste water, and is better to preserve and carry, so, generally in industrial application, the quick lime is preferentially used.
Preferably, the weight ratio of the cement to the fly ash to the slag is (1-5): (1-4): (1-3). Further preferably, the weight ratio of the waste residue, the cement, the fly ash, the slag and the broken stone is (1-2): (0.1-0.5): (0.1-0.4): (0.1-0.3): (0.4-1.5).
By adopting the technical scheme, the cement, the fly ash and the slag are used as cementing materials and are matched according to a specific proportion, so that the activity of the waste residue is favorably excited, and the waste residue is favorably and rapidly solidified. The inventor finds that when the weight ratio of the waste residue, the cement, the fly ash, the slag and the broken stone is (1-2): (0.1-0.5): (0.1-0.4): (0.1-0.3): (0.4-1.5), the curing rate is high, and the strength and water-proofing property of the obtained cured body are good. Most preferably, the weight ratio of the waste residue, the cement, the fly ash, the slag and the broken stone is 1.2: 0.2: 0.1: 0.15: 0.4.
in the application, the adopted slag is granulated blast furnace slag, and the main components are silicate and aluminate.
Crushing stone: the grain diameter is 0-15mm, and the continuous grade grading: 0-3mm (20% -30%), 3-6mm (20% -25%), 6-9mm (10% -15%), 9-13mm (10% -15%) and 12-15mm (20% -40%).
Preferably, in the step 2, when the solidified material is mixed with the waste residue, the fly ash is firstly ball-milled for 10-20min, then the fly ash is mixed with the waste residue, the cement and the water, then the ball-milling is carried out for 10-20min, and then the broken stone and the slag are added, and the mixture is uniformly stirred, pressed, molded and maintained to obtain the solidified body.
By adopting the technical scheme, the fineness of the ash content in the fly ash can be improved and the specific surface area of the ash content can be enhanced by ball milling the fly ash, so that the hydration capability of cement can be enhanced. The ball milling time affects the compressive strength of the solidified body, and the longer the ball milling time, the greater the compressive strength of the solidified body. The increase of the compressive strength of the solidified body becomes smaller as the ball milling time is increased. In practical application, considering the energy consumption increased by ball milling, in order to save cost, the ball milling time is controlled within 10-20min, so that the strength of a solidified body is improved to the greatest extent in a short time. The inventors have found that when mixing the solidified material with the waste residue, the fly ash is ball milled for 15-17min, then mixed with the waste residue, cement and water, and then ball milled for 13-15min, and the solidified body with the best strength can be prepared with the least cost.
Preferably, the curing material further comprises at least one of an early strength agent, a stabilizer, a water reducing agent and a retarder.
Further preferably, the stabilizer is selected from any one of ferric chloride, gypsum, sodium hydroxide and ferrous sulfate, and the amount of the stabilizer accounts for 0.1-0.5% of the total amount of the curing material.
Further preferably, the early strength agent is selected from triethanolamine or calcium formate, and the dosage of the early strength agent accounts for 0.03-0.1% of the weight of the cement.
Preferably, the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent, and the polycarboxylic acid high-efficiency water reducing agent accounts for 1% -3% of the cement.
Further preferably, the retarder is an alcohol retarder, the alcohol retarder is selected from any one of methanol, ethanol, propanol and ethylene glycol, and the weight of the retarder accounts for 0.5-1.7% of the weight of the cement.
By adopting the technical scheme, the water reducing agent is added to improve the fluidity of the slurry and reduce bleeding; the retarder is added, so that longer operation time can be obtained and the fluidity loss is smaller; the addition of the early strength agent can shorten the interval between the initial setting time and the final setting time; the addition of the stabilizer can improve the strength of the cured body.
In the present application, the solidification of the slag is carried out in order to obtain a solidified body which satisfies the requirements of high performance and stability, and therefore, it is considered to add an appropriate additive. Preferably, in the application, the additives are an early strength agent, a stabilizer, a water reducing agent and a retarder, and the four additives are matched with each other, so that the performance of the slurry can be improved, the performance of a cured body can be improved, and the cured body has good strength, durability, water resistance and the like.
Preferably, the solidified body obtained in the step 2 is subjected to waterproof treatment, and a waterproof layer with the thickness of 3-5mm is obtained on the surface of the solidified body after the waterproof treatment, wherein the tensile strength of the waterproof layer is 1.75-2.12 MPa.
Further preferably, the water repellent treatment comprises the steps of:
uniformly mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent, coating the mixture on the surface of a cured body, and drying;
the weight ratio of the epoxy emulsion to the epoxy curing agent is (1-1.7): (0.43-1.2);
the weight of the defoaming agent accounts for 1.3-2.7% of the weight of the epoxy emulsion.
In order to be safely landfilled, the solidified body must achieve a certain compressive strength and leaching rate. The strength of the cured body should be greater than 5MPa, preferably greater than 10MPa, because the cured body is less strong and will fracture, exposing more surface area and causing more contamination. In the application, the epoxy emulsion, the epoxy curing agent and the defoaming agent are uniformly mixed and then coated on the surface of the solidified body to obtain the waterproof layer with the thickness of 3-5mm, the tensile strength of the waterproof layer is 1.75-2.12MPa, the waterproof property of the solidified body can be greatly improved, the corrosion or damage of the environment to the solidified body is reduced, and therefore the leaching rate of the solidified body can be greatly reduced. The waterproof layer prepared according to the formula of the waterproof coating is waterproof within 0.3MPa and 30min, and the waterproof effect is good.
Preferably, in the step 1, the wastewater is oxidized by ozone or manganese oxide before the calcium source is added; after the calcium source is added, the coagulant aid is added to the waste liquid, and then solid-liquid separation is performed.
Further preferably, the coagulant aid is selected from any two of iron salt, aluminum salt and calcium salt. Further preferably, the iron salt is selected from any one of ferric chloride, ferric sulfate, polymeric ferric sulfate and ferrous sulfate; the aluminum salt is selected from any one of polyaluminium chloride, polyaluminium sulfate, aluminium trichloride and aluminium sulfate; the calcium salt is calcium chloride.
Research shows that the toxicity of trivalent arsenic is about 60 times that of pentavalent arsenic, and arsenic trioxide is commonly called arsenic trioxide and has very strong toxicity. Therefore, when the waste liquid is treated for the health of workers, ozone or oxides such as manganese oxide are added to the waste liquid to convert trivalent arsenic having high toxicity into pentavalent arsenic having low toxicity. In addition, since arsenite generally has a higher solubility than arsenate, trivalent arsenic is converted into pentavalent arsenic in the treatment of waste liquid, and the removal rate of arsenic in the waste liquid can be improved.
The adding amount of coagulant aid in the waste liquid is 10-5-10-3And the addition of the coagulant aid in mol/L is beneficial to sludge polymerization and rapid sedimentation, namely the rapid sedimentation of precipitates such as calcium arsenate, calcium fluoride, calcium arsenite and the like, so that the waste liquid treatment efficiency is improved. The inventor finds that the coagulant aid obtained by mixing polyaluminium chloride and ferric chloride according to the weight ratio of 1:0.75 has the best coagulation aid effect.
Preferably, the wastewater after solid-liquid separation is discharged after being adsorbed by an adsorbent, wherein the adsorbent is selected from one or more of nano titanium dioxide, zeolite and vermiculite.
After solid-liquid separation, the wastewater is further treated by an adsorbent, so that pollutants such as arsenic, fluorine and the like in the wastewater can be further removed, and the wastewater can be discharged up to the standard.
In summary, the present application has the following beneficial effects:
1. adding a calcium source into the waste liquid, and reacting pollutants such as arsenic, fluorine and the like in the waste liquid with the calcium source to generate precipitate; solid-liquid separation, safe discharge of waste water, interaction of waste residues and cementing materials such as cement, fly ash and slag, and quick solidification of the waste residues to form a solidified body; the solidified body is used for safe landfill, so that the safe treatment of waste residue can be realized, and secondary pollution to the environment can not be caused;
2. in the application, when the curing material is mixed with the waste residue, the fly ash is firstly ball-milled for 15-17min, then the fly ash is mixed with the waste residue, the cement and the water, and then the mixture is ball-milled for 13-15min, so that a curing body with the best strength can be prepared with the least cost;
3. according to the application, the early strength agent, the stabilizer, the water reducing agent and the retarder are matched with each other, so that the performance of the slurry can be improved, the performance of a solidified body can also be improved, and the solidified body has good strength, durability and water resistance;
4. the epoxy emulsion, the epoxy curing agent and the defoaming agent are uniformly mixed and then coated on the surface of the solidified body to form a waterproof layer, so that the waterproof property of the solidified body can be greatly improved, and the leaching rate of harmful substances such as arsenic and fluorine is reduced, thereby being beneficial to the safe landfill of the solidified body.
Detailed Description
The present application will be described in further detail with reference to examples. Specifically, the following are described: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer; the starting materials used in the following examples are all those conventionally commercially available except where specifically noted.
Raw materials
A calcium source: quick lime;
crushing stone: the particle size is 0-15mm, the continuous size grading is 0-3mm (30%), 3-6mm (20%), 6-9mm (10%), 9-13mm (15%) and 12-15mm (25%);
epoxy emulsion: epoxy emulsion E51, shandong kepler biotechnology limited;
epoxy curing agent: hebei Miyang anticorrosive materials Co., Ltd;
defoaming agent: water-based paint defoamer 302, by Haoyagei Water treatment materials, Inc.;
coagulant aid: mixing polyaluminium chloride and ferric chloride according to the weight ratio of 1: 0.75;
the initial waste liquids of examples 1 to 17 and comparative examples 1 to 2 contained arsenic in an amount of 1000 mg/L.
Example 1
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste residue, 60kg of cement, 20kg of fly ash, 20kg of slag, 100kg of broken stone and 15kg of water are mixed, pressed, molded and maintained to obtain a solidified body.
Example 2
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste slag, 7.02kg of cement, 2.34kg of fly ash, 2.34kg of slag, 11.7kg of crushed stone and 3.7kg of water are mixed, pressed, molded and cured to obtain a solidified body.
Example 3
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste slag, 26.4kg of cement, 8.8kg of fly ash, 8.8kg of slag, 44kg of crushed stone and 11.4kg of water are mixed, pressed, molded and cured to obtain a solidified body.
Example 4
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste slag, 14.7kg of cement, 14.7kg of fly ash, 14.7kg of slag, 44kg of crushed stone and 11.4kg of water are mixed, pressed, molded and cured to obtain a solidified body.
Example 5
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste slag, 18.2kg of cement, 14.6kg of fly ash, 11kg of slag, 44kg of crushed stone and 11.4kg of water are mixed, pressed, molded and cured to obtain a cured body.
Example 6
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 125.4kg of waste slag, 6.26kg of cement, 6.26kg of fly ash, 6.26kg of slag, 43.8kg of crushed stone and 4.88kg of water are mixed, pressed, molded and cured to obtain a solidified body.
Example 7
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 80kg of waste residue, 20kg of cement, 16kg of fly ash, 12kg of slag, 60kg of broken stone and 12.5kg of water are mixed, pressed, molded and maintained to obtain a solidified body.
Example 8
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 110kg of waste slag, 18.3kg of cement, 9.2kg of fly ash, 13.7kg of slag, 36.7kg of crushed stone and 10.7kg of water are mixed, pressed, molded and cured to obtain a solidified body.
Example 9
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, 9.2kg of fly ash is subjected to ball milling for 17 min; then mixing with 110kg of waste residue, 18.3kg of cement and 10.7kg of water, and then carrying out ball milling for 15 min; and then adding 36.7kg of broken stone and 13.7kg of slag, uniformly stirring, pressing and forming, and curing to obtain a solidified body.
Example 10
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, ball-milling 9.2kg of fly ash for 17min, then mixing with 110kg of waste residue, 18.3kg of cement, 10.7kg of water and 0.39kg of ferric chloride, then ball-milling for 15min, then adding 36.7kg of broken stone and 13.7kg of slag, uniformly stirring, press-molding and curing to obtain the solidified body.
Example 11
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, 9.2kg of fly ash is ball-milled for 17min, then is mixed with 110kg of waste residue, 18.3kg of cement, 10.7kg of water, 0.3kg of ferric chloride, 0.3kg of triethanolamine, 0.3kg of polycarboxylic acid high efficiency water reducing agent and 0.3kg of propanol, is ball-milled for 15min, then is added with 36.7kg of macadam and 13.7kg of slag, is uniformly stirred, is pressed and formed, and is maintained, thus obtaining the solidified body.
Example 12
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, 9.2kg of fly ash is ball-milled for 17min, then is mixed with 110kg of waste residue, 18.3kg of cement, 10.7kg of water, 0.08kg of ferric chloride, 0.02kg of triethanolamine, 0.18kg of polycarboxylic acid high efficiency water reducing agent and 0.09kg of propanol and is ball-milled for 15min, then 36.7kg of broken stone and 13.7kg of slag are added, the mixture is uniformly stirred, is pressed and formed, and is maintained, thus obtaining the solidified body.
Example 13
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, ball-milling 9.2kg of fly ash for 17min, then mixing with 110kg of waste residue, 18.3kg of cement, 10.7kg of water, 0.39kg of ferric chloride, 0.02kg of triethanolamine, 0.5kg of polycarboxylic acid high-efficiency water reducing agent and 0.31kg of propanol, ball-milling for 15min, then adding 36.7kg of broken stone and 13.7kg of slag, uniformly stirring, press-forming and maintaining to obtain a solidified body;
example 14
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, ball-milling 9.2kg of fly ash for 17min, then mixing with 110kg of waste residue, 18.3kg of cement, 10.7kg of water, 0.39kg of ferric chloride, 0.02kg of triethanolamine, 0.5kg of polycarboxylic acid high-efficiency water reducing agent and 0.31kg of propanol, ball-milling for 15min, then adding 36.7kg of broken stone and 13.7kg of slag, uniformly stirring, press-forming and maintaining to obtain a solidified body;
and step 3: and (3) carrying out waterproof treatment on the solidified body, namely uniformly mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent to obtain a waterproof coating, and then coating the waterproof coating on the solidified body, wherein the thickness of the coating is 3mm to obtain the waterproof solidified body. In the waterproof coating, the weight ratio of the epoxy emulsion to the epoxy curing agent is 1.0:0.8, and the weight of the defoaming agent accounts for 2.7 percent of the weight of the epoxy emulsion.
Example 15
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: mixing 110kg of waste residue, 18.3kg of cement, 9.2kg of fly ash, 13.7kg of slag, 36.7kg of broken stone, 10.7kg of water, 0.39kg of ferric chloride, 0.02kg of triethanolamine, 0.5kg of polycarboxylic acid high-efficiency water reducing agent and 0.31kg of propanol, performing compression molding, and maintaining to obtain a solidified body;
and step 3: and (3) carrying out waterproof treatment on the solidified body, namely uniformly mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent to obtain a waterproof coating, and then coating the waterproof coating on the solidified body, wherein the thickness of the coating is 3mm to obtain the waterproof solidified body. In the waterproof coating, the weight ratio of the epoxy emulsion to the epoxy curing agent is 1.7:1.2, and the weight of the defoaming agent accounts for 1.3% of the weight of the epoxy emulsion.
Example 16
Example 16 is different from example 15 only in that in example 16, in the water-repellent treatment, an aqueous polyurethane water-repellent paint (manufacturer: gold umbrella water-repellent material Co., Ltd.) was used, and the rest was the same as example 15.
Example 17
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding ozone into arsenic-containing waste liquid, mixing uniformly, adding quicklime with the addition amount of 1.45 times of theoretical amount, and adding 10-3A mol/L coagulant aid (polyaluminium chloride and ferric chloride are mixed according to the weight ratio of 1: 0.75), and then the solid-liquid separation is carried out to obtain waste water and waste residue; adding nano titanium dioxide into the wastewater, and directly discharging the wastewater after adsorption;
step 2: mixing 110kg of waste residue, 18.3kg of cement, 9.2kg of fly ash, 13.7kg of slag, 36.7kg of broken stone, 10.7kg of water, 0.39kg of ferric chloride, 0.02kg of triethanolamine, 0.5kg of polycarboxylic acid high-efficiency water reducing agent and 0.31kg of propanol, performing compression molding, and maintaining to obtain a solidified body;
and step 3: and (3) carrying out waterproof treatment on the solidified body, namely uniformly mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent to obtain a waterproof coating, and then coating the waterproof coating on the solidified body, wherein the thickness of the coating is 3mm to obtain the waterproof solidified body. In the waterproof coating, the weight ratio of the epoxy emulsion to the epoxy curing agent is 1.7:1.2, and the weight of the defoaming agent accounts for 1.3% of the weight of the epoxy emulsion.
Comparative example
Comparative example 1
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 44kg of waste slag, 26.4kg of cement, 8.8kg of fly ash, 8.8kg of slag, 44kg of crushed stone and 44g of water are mixed, pressed, molded and cured to obtain a solidified body.
Comparative example 2
A method for treating arsenic-containing waste liquid and solidifying arsenic slag comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: 100kg of waste slag, 44kg of cement, 44kg of crushed stone and 11.4kg of water are mixed, pressed, molded and cured to obtain a cured body.
Performance test
1. The compression strength and leaching concentration of the cured bodies or waterproof cured bodies of examples 1 to 17 and comparative examples 1 to 2 were measured, and the specific measurement results are shown in table 1 below.
The compressive strength was measured according to GB177-85, the cured bodies or waterproof cured bodies prepared in examples 1-17 and comparative examples 1-2 were cured for 7 days, and then the compressive strength of each sample was measured;
the concentration of each contaminant in the leachate was measured according to GB5086 and GB/T1555.1-11, where the concentration of arsenic in the leachate was measured according to GB 15555.3-1995 "determination of arsenic in solid waste".
TABLE 1 test chart of the properties of the cured body or the waterproof cured body
| Test specimen | Compressive strength/MPa for 7 days | Total arsenic mg/L | Fluoride mg/L |
| Example 1 | 15 | 1.2 | 0.3 |
| Example 2 | 16.5 | 1.1 | 0.2 |
| Example 3 | 19.2 | 1.1 | 0.2 |
| Example 4 | 19.5 | 1.2 | 0.2 |
| Example 5 | 21.9 | 0.9 | 0.3 |
| Example 6 | 22.5 | 0.7 | 0.2 |
| Example 7 | 22.2 | 0.6 | 0.2 |
| Example 8 | 24.5 | 0.5 | 0.2 |
| Example 9 | 25.9 | 0.4 | 0.2 |
| Example 10 | 26.1 | 0.4 | 0.2 |
| Example 11 | 26.4 | 0.5 | 0.2 |
| Example 12 | 27.2 | 0.3 | 0.1 |
| Example 13 | 27.8 | 0.2 | 0.1 |
| Example 14 | 27.4 | 0.1 | Is free of |
| Example 15 | 27.2 | 0.1 | Is free of |
| Example 16 | 27.2 | 0.18 | 0.08 |
| Example 17 | 27.0 | 0.1 | Is free of |
| Comparative example 1 | 5.7 | 2.2 | 0.9 |
| Comparative example 2 | 8.3 | 2.5 | 1.2 |
It can be seen from the combination of examples 1 to 3 and comparative examples 1 to 2 and from table 1 that the ratio of the amount of slag to the solidified material, the ratio of water to ash, the components of the solidified material, etc. all affect the strength and leaching concentration of the solidified body when the weight ratio of slag to solidified material is (1 to 3): (0.7-2), the solidified material is cement, fly ash, slag and broken stone, and when the water-cement ratio is 0.15-0.32, the strength of the prepared solidified body is high, and the leaching concentration of pollutants is low.
When the weight ratio of slag, cement, fly ash, slag and crushed stone is 2: (0.1-0.5): (0.1-0.4): (0.1-0.3): (0.4-1.5), the strength of the cured body can be enhanced; optimally, when the weight ratio of the waste residue, the cement, the fly ash, the slag and the broken stone is 1.2: 0.2: 0.1: 0.15: at 0.4, the strength of the cured product is optimal.
As can be seen by combining examples 8-9 with table 1, when the solidification material is mixed with the waste residue, the fly ash is ball-milled first, then mixed with the waste residue, cement and water, and then ball-milled, and finally crushed stone and slag are added, which is advantageous for enhancing the strength of the solidified body.
As can be seen by combining examples 10-13 with Table 1, the addition of one or more of an early strength agent, a stabilizer, a water reducer, and a retarder to the formulation improves the strength of the cured body and reduces the leaching concentration of contaminants.
It can be seen from examples 14 to 16 in combination with Table 1 that the water repellency of the cured product can be enhanced and the leaching concentration of the contaminant can be reduced by subjecting the cured product to a water repellent treatment after mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent, which is advantageous for safe landfill of the cured product.
In conclusion, it can be seen from examples 1 to 17 that the cured product with compressive strength of 15 to 27.8MPa, arsenic leaching concentration of 0.3 to 1.2mg/L and fluoride leaching concentration of 0.1 to 0.3 mg/L can be obtained by the method of the present application;
according to the hazardous waste landfill pollution control standard, the stabilization control limit of arsenic and compounds thereof (calculated by total arsenic) is 2.5mg/L, and the stabilization control limit of inorganic fluoride (excluding calcium fluoride) is 100 mg/L;
by contrast, the cured bodies produced using the method of the present application fully meet the hazardous waste landfill pollution control standards, i.e., the cured bodies of the present application can be used directly in safe landfills.
2. The quality of the raw waste liquid and the discharged waste water in examples 1 to 17 and comparative examples 1 to 2 was measured, and the specific measurement results are shown in table 2 below.
The water quality detection method comprises the following steps: atomic absorption spectrophotometry.
TABLE 2 Water quality test results table
| Detecting items | Arsenic mg/L | Fluorine mg/L | Sulfur mg/L | Magnesium mg/L |
| Original arsenic-containing waste liquid | 1000 | 100 | 20 | 8 |
| Examples 1 to 16 and comparative examples 1 to 2 | 0.35 | 0.48 | 0.1 | 0.05 |
| Example 17 | 0.18 | 0.12 | - | - |
As can be seen from the above Table 2, when the waste liquid is treated, the waste water is firstly oxidized by ozone or manganese oxide, then the calcium source is added, then the coagulant aid is added, the solid-liquid separation is carried out, and then the waste water after the solid-liquid separation is treated by the adsorbent, which is beneficial to reducing the pollutants in the waste water. The method is used for treating the arsenic-containing waste liquid, and the treated waste water reaches the discharge standard and can be directly discharged.
As can be seen from tables 1 and 2, the calcium source is added into the waste liquid, and pollutants such as arsenic and fluorine in the waste liquid react with the calcium source to generate a precipitate; solid-liquid separation, safe discharge of waste water, interaction of waste residue with cementing materials such as cement, fly ash and slag, quick solidification of waste residue to obtain solidified bodies, and direct application of the solidified bodies in safe landfill. When pollutants such as arsenic, fluorine in the waste water are got rid of to this application, directly be used for safe landfill with the waste residue, can not cause secondary pollution.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (2)
1. A method for treating arsenic-containing waste liquid and solidifying arsenic slag is characterized in that: the method comprises the following steps:
step 1: adding quicklime into the arsenic-containing waste liquid, wherein the adding amount of the quicklime is 1.45 times of the theoretical amount, and then carrying out solid-liquid separation to obtain waste water and waste residue;
step 2: firstly, 9.2kg of fly ash is ball-milled for 17min, then is mixed with 110kg of waste residue, 18.3kg of cement, 10.7kg of water, 0.39kg of ferric chloride, 0.02kg of triethanolamine, 0.5kg of polycarboxylic acid high efficiency water reducing agent and 0.31kg of propanol and is ball-milled for 15min, then 36.7kg of broken stone and 13.7kg of slag are added, the mixture is uniformly stirred, is pressed and formed, and is maintained, thus obtaining the solidified body.
2. The method for treating arsenic-containing waste liquid and solidifying arsenic slag as claimed in claim 1, wherein: also comprises the following steps: and step 3: carrying out waterproof treatment on the solidified body, namely uniformly mixing the epoxy emulsion, the epoxy curing agent and the defoaming agent to obtain a waterproof coating, and then coating the waterproof coating on the solidified body, wherein the thickness of the coating is 3mm to obtain a waterproof solidified body; in the waterproof coating, the weight ratio of the epoxy emulsion to the epoxy curing agent is 1.0:0.8, and the weight of the defoaming agent accounts for 2.7 percent of the weight of the epoxy emulsion.
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| CN106987194A (en) * | 2017-04-14 | 2017-07-28 | 华南理工大学 | A kind of non-ion aqueous epoxy resin latex and nonionic waterborne epoxy curing agent and its preparation method and aqueous epoxy resins varnish |
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| CN102249609B (en) * | 2011-04-29 | 2013-06-12 | 昆明理工大学 | Arsenic-containing waste slag solidified body and preparation method thereof |
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